1. Field of the Invention
The present invention relates to a superconducting thin film and a method for preparing the same. More particularly, it relates to a superconducting thin film composed of compound oxide having a high critical temperature and also possessing lasting stability for a long period and a method for preparing the same.
2. Description of the Related Art
The superconductivity is a phenomenon which is explained to be a phenomenon of a kind of phase change of electrons under which the electrical resistance become zero and the perfect diamagnetism is observed. Thus, under the superconducting condition, electric current of a very high current density can be delivered without any loss of power.
Therefore, if the superconducting power cable is realized, the power loss of about 7% which is inevitable in the conventional power cables can be reduced sharply. Realization of superconducting coils which can generate a very high magnetic field is expected to accelerate development in the field of fusion power generation in which the electric power is consumed beyond its output under the present technology, as well as in the field of MHD power generation or motor-generators. The development of superconductivity are demanded also in other industrial fields such as in the field or electric power reservation; in the field of transportation for example magnetic levitation trains, or magnetically propelling ships; in the medical field such as high-energy beam radiation unit; or in the field of science such as NMR or high-energy physics.
In addition to the abovementioned electric power applications, the superconducting materials can be used in the field of electronics, for example, as a device using the Josephson effect in which quantum efficiency is observed macroscopically when an electric current is passed through a weak junction arranged between two superconductors. Tunnel junction type Josephson device which is a typical application of the Josephson effect is expected to be a high-speed and low-power consuming switching device owing to smaller energy gap of the superconducting material. It is also expected to utilize the Josephoson device as a high sensitive sensors or detectors for sensing very weak magnetic field, microwave, radiant ray or the like since variation of electromagnetic wave or magnetic field is reflected variation of Josephson effect and can be observed as a quantum phenomenon precisely. Development of the superconducting devices is also demanded in the field of high-speed computers in which the power consumption per unit area is reaching to the upper limit of the cooling capacity with increment of the integration density in order to reduce energy consumption.
However, the critical temperature could not exceed 23.2K of Nb.sub.3 Ge which was the highest Tc for all studies for the past ten years. The possibility of an existence of new types of superconducting materials having much higher Tc was revealed by Bednorz and Muller, who discovered a new oxide type superconductor in 1986 [Z. Phys. B64 (1986) 189]
It had been known that certain ceramics material of compound oxides exhibit the property of superconductivity. For example, U.S. Pat. No. 3,932,315 discloses Ba-Pb-Bi type compound oxide which shows superconductivity and Japanese patent laid-open No. 60-173,885 discloses that Ba-Bi type compound oxides also show superconductivity. These superconductors, however, possess rather lower transition temperature of about 10K and hence usage of liquidized helium (boiling point of 4.2K) as cryogen is indispensable to realize superconductivity.
The new type compound oxide superconductor discovered by Bednorz and Muller is represented by [La,Sr].sub.2 CuO.sub.4 which is called as the K.sub.2 NiF.sub.4 -type oxide having a crystal structure which is similar to known perovskite type oxides. The K.sub.2 NiF.sub.4 -type oxides show such higher Tc as 30K, which are extremely higher than known superconducting materials.
It was also reported that C. W. Chu et al discovered, in the United States of America, another superconducting material so called YBCO type represented by YBa.sub.2 Cu.sub.3 O.sub.7-x having the critical temperature of in the order of 90K in Feb. 1987. Still other type new superconducting materials which were reported recently are a compound oxide of Bi-Sr-Ca-Cu-O system and Tl-Ba-Ca-Cu-O system which exhibit such high Tc as more than 100K and which are chemically mush stable than the abovementioned YBCO type compound oxide or the like.
And hence, the possibility of existence of high-temperature superconductors have burst onto the scene.
The new type superconductor of compound oxide, however, is not stable, and hence their superconductivity is lost or deteriorated with the passing of time. In fact, there is such a tendency that their critical temperature and critical current density drop gradually with the passing of time. This tendency is noticeable in case of a thin film prepared by physical vapour deposition technique. This fact is explained by defectiveness of oxygen deficiency, in other words, imperfect oxygen contents in the crystal. It is known that the superconducting property of compound oxide is influenced by the oxygen contents or oxygen deficiency in their crystalline structures. In order to overcome such drawback, it is usual practice that the deposited thin film prepared by the physical vapour deposition technique is heat-treated or annealed, particularly in the final stage of preparation, under a higher partial pressure of oxygen gas. In fact, if the deposited thin film is not heat-treated, its superconducting property is very poor.
However, even if the deposited thin film is heat-treated, it is impossible to prevent the thin film from deterioration of superconducting property which occur with the passing of time. Such deterioration may be caused by the abovementioned defectiveness of oxygen deficiency resulting from that the compound oxide react with water in air and that oxygen in the crystal escape with the passing of time or so on, so that quasi-stable phase of the superconducting compound oxide is transformed to a non-superconducting phase. The deterioration of superconductivity, in other words a phenomenon that the superconducting property is lost gradually in time is a big problem of compound oxide type superconductors in their actual use.
Therefore, an object of the present invention is to overcome the abovementioned problems of the conventional technique and to provide a superconducting thin film improved in stability during storage or during actual use and a method for preparing the same.